Quantifying the Effect of Basic Minerals on Acid- and Ligand-Promoted Dissolution Kinetics of Iron in Simulated Dark Atmospheric Aging of Dust and Coal Fly Ash Particles.

The content and multiphase chemistry of iron (Fe) in multicomponent atmospheric aerosols are important to global climate and oceanic models. To date, reported dissolution rates of Fe span orders of magnitude with no quantifiable dependency on the content of basic minerals that coexist with Fe. Here, we report dissolution rates of Fe in simulated dark atmospheric aging of fully characterized multielement particles under acidic conditions (bulk pH 1 or 3) with and without oxalic acid and pyrocatechol. Our main findings are (a) the total amount of Ca and Mg was higher in coal fly ash than in Arizona test dust, (b) Fe dissolution initial rates increased exponentially with %Ca/Al and %Mg/Al below 50%, (c) a reduction in the Fe dissolution initial rate was observed with %Ca/Al higher than 50%, (d) reactive Ca and Mg minerals increased the calculated initial pH at the liquid/solid interface to values higher by only 1.5-2 units than the measured bulk pH, yet interfacial water remained acidic for Fe dissolution to take place, and (e) reactive Ca and Mg minerals enhanced the deprotonation of organics at the interface, aiding in ligand-promoted dissolution of Fe. The impact of these results is discussed within the context of constraining Fe dissolution kinetic models.